Coating material for electronic components

ABSTRACT

The invention relates to novel polyhydroxyamide compounds that, in the form of their oxazoles, ane suited as a coating material, particularly for electronic components. The invention also relates to a method for producing these novel compounds and to the use thereof.

[0001] The present invention relates to novel polyhydroxyamide compoundswhich, in the form of their oxazoles, are suitable as a coatingmaterial, in particular of electronic components, a process for theirpreparation and their use.

BACKGROUND OF THE INVENTION AND PRIOR ART

[0002] In microelectronics, highly heat-resistant polymers are requiredas protective and insulating coats. These polymers can be used as adielectric between chip and metalization or between two metal planes ofthe chip, e.g. in multichip modules, memory chips and logic chips. Themetal planes may be present below or above the inorganic passivation ofthe chip. Moreover, such polymers can also be used as a buffer coatingbetween the chip and its housing. Among these polymers, thepolyhydroxyamides have good solubility in organic solvents and good filmformation properties and can be applied to the electronic components bymeans of the economical spin-coating technique. These polyhydroxyamidesare cyclized after a thermal treatment (curing) to give polybenzoxazolesand, according to the following equation, thus acquire their finalproperties:

[0003] The requirements with respect to the end product are, forexample, good insulation properties and sufficient thermal stability.Good adhesion of the material to all relevant substrates, for examplesilica, silicon nitride, titanium, titanium nitride, tantalum ortantalum nitride, is also particularly important. Titanium, titaniumnitride, tantalum and tantalum nitride are proven adhesion-promoting andbarrier coats for aluminum or copper metalizations.

[0004] If the polymer is used as an insulating coat, for example belowthe uppermost coat of metal, i.e. the outer wiring, further propertiesare important. These are in particular the adhesion of the metallicconductors or of the corresponding adhesion-promoting and barrier coatsto the insulating coat and high resilience or extensibility of thisinsulating coat so that the different expansions of the chip and of thecircuit board are compensated. FIG. 1 shows a flip-chip contact, whereinthe upper part of the chip points toward the circuit board. Theabovementioned properties are, however, also important in othermetalization coats of the chip.

[0005] Polyhydroxyamides which are readily soluble and have good thermalstability are described, for example, in EP 0 317 942 A2, DE 3 718 212A1 or U.S. Pat. No. 5,077,378. However, the materials described in thesepublications have very low resilience or elongation and only moderateadhesion, in particular to titanium nitride or tantalum nitride.

[0006] Chemical Abstracts Vol. 83, 1975, report 81475x describes coatingmaterials for cables, but these are not polyhydroxyamides.

[0007] Patent Abstracts of Japan C-991, Oct. 2, 1992, Vol. 16/No. 473describes fluorinated aromatic polyhydroxyamides and polybenzoxazoleshaving high thermal stability. Particular adhesion properties of thesecompounds are not mentioned.

[0008] It is an object of the present invention to provide readilysoluble polyhydroxyamides which, after application to a substrate anddrying, if required with a thermal treatment, form a heat-stable andhighly resilient coat with very good adhesion to metallic andnonmetallic substrates.

[0009] It is a further object of the present invention to provideelectronic components which have heat-stable and highly resilient coatswith very good adhesion to metallic and nonmetallic substrates.

[0010] This object is achieved, according to the invention, bypolyhydroxyamide compounds as claimed in claim 1. Preferred embodimentsof the invention are evident from the description and the subclaims.

[0011] The present invention furthermore relates to polybenzoxazoleswhich are obtained by cyclization of hydroxyamide units of thepolyhydroxyamides according to the invention, and their use.

[0012] The invention also includes electronic components which have thepolybenzoxazole coats according to the invention.

[0013] The present invention furthermore relates to a preparationprocess for the polyhydroxyamides according to the invention and thecorresponding polybenzoxazoles thereof.

[0014] The invention furthermore includes compositions which contain thepolyhydroxyamides according to the invention and an organic solvent.

DESCRIPTION

[0015] The present invention relates to novel polyhydroxyamides andpolybenzoxazoles derived therefrom by cyclization. In the form of theirpolybenzoxazoles, the compounds according to the invention can be usedfor coating substrates, in particular electronic components.

[0016] According to the invention, compounds of the following formula Ior II are claimed:

[0017] in which:

[0018] a=0 or 1, with the proviso that, if a is 0, c must be ≧1,

[0019] b=0-100,

[0020] c=0-50, with the proviso that, if c is 0, a must be =1,

[0021] d=1-100,

[0022] e=0-100,

[0023] f=0-100,

[0024] g=0-50,

[0025] h=0-100,

[0026] k=0-100,

[0027] m=0-100,

[0028] n=0-50,

[0029] p=0 or 1;

[0030] in which:

[0031] q=1-100,

[0032] r=1-100,

[0033] s=0-100,

[0034] t=0-100,

[0035] u=0-100,

[0036] v=0-50,

[0037] w=0-100,

[0038] x=0-100,

[0039] y=0-100,

[0040] z=0-50;

[0041] X, independently of one another, are:

[0042] in which R1 [sic] in each case may be identical to or differentfrom R2 [sic] and α is 0-100 and β is 0-100, α and β not simultaneouslybeing 0;

[0043] R₁ and R₂ are:

[0044] substituted or unsubstituted alkylene, arylene or cycloalkylenegroups;

[0045] Q is —O—, —S— and/or —NH—;

[0046] A₁ and/or A₂, where A₁ may be identical to or different from A₂if A₁ and/or A₂ are bonded to Q or —NH—, are:

[0047] H, substituted or unsubstituted alkylcarbonyl, alkenylcarbonyl,cycloalkenylcarbonyl, arylcarbonyl, aralkylcarbonyl, aralkenylcarbonylor aralkynylcarbonyl, it being possible for the carbonyl group to bebonded to the aromatic or to the alkyl or alkenyl or alkynyl group;

[0048] A₁ and/or A₂, where A₁ may be identical to or different from A₂if A₁ and/or A₂ are bonded to —CO—, are:

[0049] hydroxyl, substituted or unsubstituted alkoxy, alkenyloxy,aryloxy, cycloalkenyloxy, amino, alkylamino, alkenylamino, arylamino,arylalkenyloxy, arylalkylamino;

[0050] A₃ is:

[0051] H, substituted or unsubstituted alkylcarbonyl, alkenylcarbonyl,cycloalkenylcarbonyl, arylcarbonyl, aralkylcarbonyl, aralkenylcarbonylor aralkynylcarbonyl, it being possible for the carbonyl group to bebonded to the aromatic or to the alkyl or alkenyl or alkynyl group;

[0052] Y₁ and Y₂, where Y₁ may be identical to or different from Y₂,are:

[0053] substituted or unsubstituted aryl, a substituted or unsubstitutedpolynuclear aromatic hydrocarbon compound, substituted or unsubstitutedalkyl, alkenyl, alkynyl, aryl or aralkyl, aralkenyl, aralkynyl;

[0054] Z₁ and Z₂, where Z₁ may be identical to or different from Z₂,are:

[0055] aryl, aralkyl, aralkenyl, aralkynyl, heteroaryl or a polynucleararomatic hydrocarbon compound.

[0056] According to the invention, X₁ to X₆ may be identical to ordifferent from one another. According to the invention,polyhydroxyamides where X=X₁ and/or X=X₃ are preferred. It isfurthermore preferred according to the invention if, in X, α is 0-10and/or β is 0-10. In the polyhydroxyamides according to the invention,it is preferable if, in formula I, b=0-20, c=0-10, d=4-40, e=0-20,f=0-20, g=0-10, h=0-20, k=0-20, m=0-20 and/or n=0-10;

[0057] and in formula II, q=3-40, r=1-40, s=0-40, t=0-20, u=0-20,v=0-10, w=0-20, x=0-20, y=0-20 and/or z=0-10.

[0058] According to the invention, polyhydroxyamides in which R₁ and/orR₂ have the following meaning are furthermore preferred:

—(CH₂)_(χ)—

[0059] χ=1-20

[0060] where δ=0-20, ε=0-20, and R₃ and R₄: —H, —(CH₂)_(φ)—CH₃;

[0061] φ=0-10 or —OH, where R₃ and R₄ cannot simultaneously be —OH

[0062] The following radicals are particularly preferred for R₁ and/orR₂:

—(CH₂)_(χ)—

[0063] χ=1-20

[0064] where δ=0-20, ε=0-20, and R₃ and R₄: —H, —(CH₂)_(φ)—CH₃;

[0065] φ=0-10 or —OH, where R₃ and R₄ cannot simultaneously be —OH

[0066] According to the invention, Q is preferably —O— and/or —NH—,furthermore preferably —O— and —NH—.

[0067] According to the invention, further preferred polyhydroxyamidesare those in which A₁ and/or A₂, if A₁ and/or A₂ are bonded to Q or—NH—, and A₃ have the following meaning:

[0068] where φ=0-10 and W═—CN, —C(CH₃)₃, —(CH₂)_(φ)—CH₃, —(CF₂)₁₀₀ —CF₃,—O—(CH₂)₁₀₀ —CH₃, —O—(CF₂)_(φ)—CF₃,

—CH═CH₂, —C≡CH or

[0069] Among these, the following are particularly preferred:

[0070] If A₁ and/or A₂ are bonded to —CO—, A₁ and/or A₂ preferably havethe following meaning:

[0071] where φ=0-10 and W=—CN, —C(CH₃)₃, —(CH₂)_(φ)—CH₃, —(CF₂)_(φ)—CF₃,—O—(CH₂)_(φ)—CH₃, —O—(CF₂)_(φ)—CF₃,

—CH═CH₂, —C≡CH or

[0072] Among these, the radicals —OH and —NH₂ are particularlypreferred.

[0073] Y₁ and Y₂, where Y₁ may be identical to or different from Y₂, arepreferably:

[0074] Y₁ and/or Y₂ are particularly preferably:

[0075] According to the invention, preferred polyhydroxyamides are thosein which the radical

[0076] R₅ in Y₁ and/or Y₂ is —H, —CN, —C(CH₃)₃, —(CH₂)_(φ)—CH₃,—(CF₂)_(φ)—CF₃, —O—(CH₂)_(φ)'CH₃, —O—(CF₂)_(φ)—CF₃ and/or is:

[0077] where φ=0-10 and W=—CN, —C(CH₃)₃, —(CH₂)_(φ)—CH₃, —(CF₂)_(φ)—CF₃,—O—(CH₂)_(φ)—CH₃, —O—(CF₂)_(φ)—CF₃,

—CH═CH₂, —C≡CH or

[0078] Particularly preferred radicals R₅ are:

—C≡CH

[0079] According to the invention, R₆ in Y₁ and/or Y₂ is preferably —O—,—CO—, —NR₇—, —S—, —SO₂—, —S₂—, —CH₂— or:

—C═C— —C≡C—

[0080] Particularly preferred radicals R₆ among these are: —O—, —CO—,—NR₇—, —CH₂— and:

—(CF₂)_(η)—

[0081] η=1-10

[0082] According to the invention, R₇ in Y₁ and/or Y₂ is preferably —Hand/or:

—(CH₂)_(φ)—CH₃

[0083] (φ=0-10)

—(CF₂)_(φ)—CF₃

[0084] (φ=0-10)

[0085] When it denotes R₆, R₈ is, according to the invention, preferablyalkyl having 1 to 10 carbon atoms or aryl.

[0086] According to the invention, Z₁ and Z₂ are preferably thefollowing radicals, it being possible for Z₁ to be identical to ordifferent from Z₂:

[0087] Here, R₆ is defined as above.

[0088] Particularly preferred radicals Z₁ and/or Z₂ are:

[0089] The polyhydroxyamides according to the invention can besubstantially controlled with respect to the indices by thestoichiometry of the reactants or the prepolymerization. Thecharacterization of the polyhydroxyamides is expediently effected bymeans of ¹H-NMR, gel permeation chromatography (GPC) and/orthermogravimetry (TGA). On the basis of the different chemical shifts ofindividual protons of the individual components and the correspondingintegrals, the indices of the individual components can be substantiallydetermined via the molar mass distribution of the polymer (obtained byGPC).

[0090] The polyhydroxyamides of the present invention can also beconverted into polybenzoxazoles by cyclization of hydroxyamide units.According to the invention, polybenzoxazoles are to be understood asmeaning those compounds which are obtained by cyclization of thehydroxyamide units of the compounds according to the invention.According to the invention, the term includes not only oxazole ringswhich are present in the vicinity of phenyl rings but alternatively alsothose compounds in which the oxazole ring is present, for example, inthe vicinity of thiophene or furan rings.

[0091] These polybenzoxazoles also included according to the inventionhave outstanding adhesion to metallic and nonmetallic substrates, inparticular to in the [sic] silica, silicon nitride, titanium, titaniumnitride, tantalum or tantalum nitride. The polybenzoxazoles according tothe invention are moreover extremely heat-resistant and can be used asprotective and/or insulating coats in microelectronics. A furtherparticular advantage is the high resilience or extensibility of thepolybenzoxazole insulating coats of the present invention. The followingmay be mentioned as examples of electronic components which have apolybenzoxazole coat according to the invention: flip-chips, memorychips, logic chips, flash memories, multichip modules, circuit boards,microprocessors, embedded DRAMs.

[0092] The polyhydroxyamides according to the invention can be preparedby conventional processes. Here, a compound of the formula Z₁(NH₂)₂(OH)₂and/or Z₂(NH₂)₂(OH)₂ is reacted with a compound of the formula Y₁(COCl)₂and/or Y₂(COCl)₂, which is preferably used in excess, and the productobtained is then reacted with a compound of the formula X(QOH)₂ orX(QNH₂)₂ and the product obtained thereby is then optionally reactedwith a precursor compound for A₁, A₂ and/or A₃, A₁, A₂ and/or A₃ beingbonded at the chain ends. Here, Z₁, Z₂, Y₁, Y₂, X, A₁, A₂ and A₃ aredefined as above. The fact that A₁, A₂ and/or A₃ are bonded at the chainends is evident simply from the fact that the products can be completelycyclized. Products which cannot be completely cyclized are still partlysoluble after the cyclization treatment, i.e. swell, which does notoccur in the case of completely cyclized products.

[0093] For the synthesis of copolymers where Y₁ is different from Y₂, amixture of Y₁(COCl)₂ and Y₂(COCl)₂ can be reacted with Z₁(NH₂)₂(OH)₂ orZ₂(NH₂)₂(OH)₂, the stoichiometry of total Y being appropriatelydistributed over Y₁ and Y₂. A reaction with X(QOH)₂ or X(QNH₂)₂ is theneffected.

[0094] Another possibility for the preparation of copolymers mixed withrespect to Z₁, Z₂, Y₁ and Y₂ is to prepolymerize two separate batches inwhich, for example, on the one hand Y₁ and Z₁ and on the other hand Y₂and Z₂ are combined. The two batches are then combined and arepolymerized with X(OH)₂. Blocks, for example according to the scheme-Z₁Y₁—X—Y₂-Z₂-, can thus be prepared in a defined manner.

[0095] The synthesis gives straight-chain polyhydroxyamides, as can beshown by ¹H-NMR spectroscopy (cf. example 4 and FIG. 2). Moreover,crosslinked chains would not give good solubility, as in the examplesaccording to the invention.

[0096] The conversion of polyhydroxyamides into polybenzoxazoles isusually effected by a thermal treatment (curing). This thermal treatmentis effected, according to the invention, at 250-450° C., preferably300-400° C., most preferably at about 300-350° C.

[0097] The thermal treatment usually takes 0.5-3 hours, preferably 1-3hours, most preferably 1-2 hours.

[0098] The invention also relates to a process for coating substrates,the polyhydroxyamides according to the invention being applied to thesubstrate to be coated, and the coated substrate then being heated inorder to form a polybenzoxazole coat on the substrate. During theheating, the above parameters for the thermal treatment are preferablyused.

[0099] The polymers according to the invention are readily soluble inmany organic solvents, e.g. acetone, cyclohexanone, diethylene glycolmono- or diethyl ether, N-methylpyrrolidone, γ-butyrolactone, ethyllactate, tetrahydrofuran or ethyl acetate, and can be applied withoutproblems to substrates by means of conventional methods, for example thespin coating technique. After the thermal treatment (curing) of thesubstrate provided with the polyhydroxyamides, the film obtainedexhibits substantially higher resilience or extensibility andsubstantially better adhesion to various substrates, in particular totitanium, titanium nitride, tantalum and tantalum nitride, in comparisonwith other comparable materials.

[0100] The invention also relates to compositions which contain thepolyhydroxyamides according to the invention in an organic solvent,preferably in one of the solvents acetone, cyclohexanone, diethyleneglycol mono- or diethyl ether, N-methylpyrrolidone, γ-butyrolactone,ethyl lactate, tetrahydrofuran, ethyl acetate or mixtures thereof.According to the invention, compositions in which the polyhydroxyamideis present in an amount of 10-50% by weight, more preferably 20-40% byweight, most preferably about 20% by weight, based on the totalcomposition, are preferred.

[0101] The substrates which were coated using the novel materialaccording to the invention withstand a substantially larger number ofthermal cycles than those which were produced using materials accordingto the prior art. Suitable substrates for the polymers according to theinvention are, for example, silicon chips (1) which have the insulatingmaterial (2) according to the invention with a metal coat (3) presentthereon and are (spot) soldered (5) or adhesively bonded with aconductive adhesive to a circuit board (4) (cf. FIG. 1).

[0102] The polybenzoxazole coats according to the invention preferablyserve, according to the invention, as protective and/or insulating coatsin electrical components.

[0103] The invention is described in more detail below with reference toembodiments. However, these are not intended to limit the scope of thepresent invention.

FIGURES

[0104]FIG. 1 shows the structure of a flip-chip contact.

[0105]FIG. 2 shows a 1H-NMR spectrum of the polyhydroxyamide fromexample 4.

EXAMPLES Chemicals Used Bisaminophenols9,9′-Bis(4-((3-hydroxy-4-amino)phenoxy)phenyl)fluorene[sic]—(bisaminophenol 1)

[0106]

2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane—(bisaminophenol 2)

[0107]

3,3′-Diamino-4,4′-dihydroxybiphenyl—(bisaminophenol 3)

[0108]

Bisaminophenol 4

[0109]

Bisaminophenol 5: 3,3′-dihydroxybenzidine

[0110]

Dicarboxylic acid chlorides 5-Ethynylisophthaloyl chloride—(dicarboxylicacid chloride 1)

[0111]

4,4′-Di(chlorocarbonyl)diphenyl ether—(dicarboxylic acid chloride 2)

[0112]

Terephthaloyl chloride—(dicarboxylic acid chloride 3)

[0113]

Isophthaloyl chloride—(dicarboxylic acid chloride 4)

[0114]

1,8-Anthracenedicarboxylic acid chloride (dicarboxylic acid chloride 5)

[0115]

2,6-Naphthalenedicarboxylic acid chloride (dicarboxylic acid chloride 6)

[0116]

Endcap cis-5-Norbornene-endo-2,3-dicarboxylic anhydride—(endcap 1)

[0117]

Methacryloyl chloride (endcap 2)

[0118]

Bishydroxycarbonates UC-Carb 100 (UBE Industries,LTD.)—(bishydroxycarbonate 1)

[0119]

[0120] n=3-6

UH-Carb 300 (UBE Industries, LTD.)—(bishydroxycarbonate 2)

[0121]

[0122] n=10-14

Bishydroxyester Poly[di(ethylene glycol)phthalate]diol—(bishydroxyester1)

[0123]

[0124] n=2-4

Bishydroxyether Poly(ethylene glycol-co-propylene glycol)-polyether 1

[0125] M=2 500 g/mol

[0126] n=10-80

Synthesis of polyhydroxyamides according to the invention (examples 1-9)Example 1 Polyhydroxyamide 1

[0127] 10 g (17.7 mmol) of bisaminophenol 1 are dissolved in 100 ml ofdistilled N-methylpyrrolidone (NMP). A solution of 4.83 g (21.25 mmol)of dicarboxylic acid chloride 1 in 50 ml of distilled γ-butyrolactone(γ-BL) is added dropwise to this solution at 10° C. while stirring.Stirring is continued for a further hour at 10° C. and then for 1 hourat 20° C. A solution of 7.08 g (7.08 mmol) of bishydroxycarbonate 1 in60 ml of distilled NMP is then added dropwise at 10° C. The reactionsolution is stirred for a further 1.5 hours at 10° C. and then for 12hours at 20° C. After cooling again to 10° C., 5.4 g (52.3 mmol) oftriethylamine, dissolved in 20 ml of NMP, are added to the reactionmixture, which is warmed up to room temperature and stirred for 2 hours.

[0128] In order to isolate the polymer, the reaction mixture is filteredand the filtrate is added dropwise to 2 500 ml of 2-propanol. Theprecipitated polymer is filtered off with suction and washed twice in 1000 ml portions of cold demineralized water and once in 2 000 ml ofdemineralized water at 80° C., filtered off, and dried for 72 hours at50° C./10 mbar. The yield is 19.3 g.

[0129] The polyhydroxyamide prepared in this manner is readily solublein solvents such as NMP, γ-BL, tetrahydrofuran, cyclohexanone,cyclopentanone and diethylene glycol monomethyl ether.

Example 2 Polyhydroxyamide 2

[0130] 183.13 g (0.5 mol) of bisaminophenol 2 are dissolved in 600 ml ofdistilled NMP. A solution of 177.07 g (0.6 mol) of dicarboxylic acidchloride 2 in 550 ml of distilled γ-BL is added dropwise to thissolution at 10° C. while stirring. Stirring is effected for 1 hour at10° C. and then for 1 hour at 20° C. A solution of 115.12 g (0.2 mol) ofbishydroxyester 1 in 250 ml of distilled γ-BL is then added dropwise at10° C. The reaction solution is stirred for a further 1.5 hours at 10°C. and then for 12 hours at 20° C. After cooling again to 10° C., 129.4g (1.6 mol) of pyridine, dissolved in 450 ml of γ-BL, are added to thereaction mixture, which is warmed up to room temperature and stirred for2 hours.

[0131] In order to isolate the polymer, the reaction mixture is filteredand the filtrate is added dropwise to a mixture of 3 000 ml ofdemineralized water and 1 000 ml of 2-propanol. The precipitated polymeris filtered off with suction and washed twice in 2 000 ml portions ofcold demineralized water and once in 1 000 ml of demineralized water at80° C., filtered off, and dried for 72 hours at 50° C./10 mbar. Theyield is 356.7 g.

[0132] The polyhydroxyamide prepared in this manner is readily solublein solvents such as NMP, γ-BL, tetrahydrofuran, cyclohexanone,cyclopentanone and diethylene glycol monomethyl ether. The molar mass ofthe polyhydroxyamide 2 is about 42 000 (GPC). This gives the followingvalues for the coefficients of the general formula for this example:a=1; b-k=0; m=70-80 (based on the molar mass distribution); n=0; p=1.

Example 3 Polyhydroxyamide 3

[0133] 6.14 g (28.37 mmol) of bisaminophenol 3 are dissolved in 100 mlof distilled NMP. A solution of 7.00 g (30.83 mmol) of dicarboxylic acidchloride 1 in 50 ml of distilled γ-BL is added dropwise to this solutionat 10° C. while stirring. Stirring is effected for a further hour at 10°C. and then for 1 hour at 20° C. A solution of 6.79 g (3.39 mmol) ofbishydroxycarbonate 2 in 60 ml of distilled NMP is then added dropwiseat 10° C. The reaction solution is stirred for a further 1.5 hours at10° C. and then for 12 hours at 20° C. After cooling again to 10° C.,7.78 g (77.10 mmol) of triethylamine, dissolved in 20 ml of NMP, areadded to the reaction mixture, which is warmed up to room temperatureand stirred for 2 hours.

[0134] In order to isolate the polymer, the reaction mixture is filteredand the filtrate is added dropwise to 1 500 ml of 2-propanol. Theprecipitated polymer is filtered off with suction and washed twice in 2000 ml portions of cold demineralized water and once in 1 000 ml ofdemineralized water at 80° C., filtered off, and dried for 72 hours at50° C./10 mbar. The yield is 17.74 g.

[0135] The polyhydroxyamide prepared in this manner is readily solublein solvents such as NMP, γ-BL, tetrahydrofuran, cyclohexanone,cyclopentanone and diethylene glycol monomethyl ether.

Example 4 Polyhydroxyamide 4

[0136] 5.00 g (8.86 mmol) of bisaminophenol 1 are dissolved in 70 ml ofdistilled N-metylpyrrolidone [sic] (NMP). A solution of 2.25 g (11.07mmol) of dicarboxylic acid chloride 3 in 50 ml of distilledγ-butyrolactone (γ-BL) is added dropwise to this solution at 10° C.while stirring. Stirring is effected for a further hour at 10° C. andthen for 1 hour at 20° C. A solution of 2.55 g (4.43 mmol) ofbishydroxyester 1 in 40 ml of distilled NMP is then added dropwise at10° C. The reaction solution is stirred for a further 1.5 hours at 10°C. and then for 12 hours at 20° C. After cooling again to 10° C., 2.78 g(27.5 mmol) of triethylamine, dissolved in 20 ml of γ-BL, are added tothe reaction mixture, which is warmed up to room temperature and stirredfor 2 hours. In order to isolate the polymer, the reaction mixture isfiltered and the filtrate is added dropwise to 1 500 ml of 2-propanol.The precipitated polymer is filtered off with suction and washed twicein 1 000 ml portions of cold demineralized water and once in 1 000 ml ofdemineralized water at 80° C., filtered off, and dried for 72 hours at50° C./10 mbar. The yield is 8.92 g. The polyhydroxyamide prepared inthis manner is readily soluble in solvents such as NMP, γ-BL,tetrahydrofuran, cyclohexanone, cyclopentanone and diethylene glycolmonomethyl ether.

[0137]FIG. 2 shows a ¹H-NMR spectrum of the polyhydroxyamide 4 prepared.The presence of phenolic protons shows that the bishydroxyester 1 doesnot react with the phenolic protons of the bisaminophenol, i.e.unbranched chains form and not crosslinked products. Crosslinkedproducts would also not have the good solubility like the productsaccording to the invention.

Example 5 Polyhydroxyamide 5

[0138] 183.12 g (0.5 mol) of bisaminophenol 2 are dissolved in 600 ml ofdistilled NMP. A solution of 177.07 g (0.6 mol) of dicarboxylic acidchloride 2 in 550 ml of distilled γ-BL is added dropwise to thissolution at 10° C. while stirring. Stirring is effected for a furtherhour at 10° C. and then for 1 hour at 20° C. A solution of 400.6 g (0.2mol) of bishydroxycarbonate 2 in 250 ml of distilled γ-BL is then addeddropwise at 10° C. The reaction solution is stirred for a further 1.5hours at 10° C. and then for 12 hours at 20° C. After cooling again to10° C., 129.4 g (1.6 mol) of pyridine, dissolved in 450 ml of γ-BL, areadded to the reaction mixture, which is warmed up to room temperatureand stirred for 2 hours.

[0139] In order to isolate the polymer, the reaction mixture is filteredand the filtrate is added dropwise to a mixture of 3 000 ml ofdemineralized water and 1 000 ml of 2-propanol. The precipitated polymeris filtered off with suction and washed twice in 2 000 ml portions ofcold demineralized water and once in 1 000 ml of demineralized water at80° C., filtered off, and dried for 72 hours at 50° C./10 mbar. Theyield is 342.3 g.

[0140] The polyhydroxyamide prepared in this manner is readily solublein solvents such as NMP, γ-BL, tetrahydrofuran, cyclohexanone,cyclopentanone and diethylene glycol monomethyl ether.

Example 6 Polyhydroxyamide 6

[0141] 7.89 g (36.49 mmol) of bisaminophenol 3 are dissolved in 100 mlof distilled NMP. A solution of 8.00 g (39.40 mmol) of dicarboxylic acidchloride 4 in 50 ml of distilled γ-BL is added dropwise to this solutionat 10° C. while stirring. Stirring is effected for a further hour at 10°C. and then for 1 hour at 20° C. A solution of 7.50 g (13.02 mmol) ofbishydroxyester 1 in 60 ml of distilled NMP is then added dropwise at10° C. The reaction solution is stirred for a further 1.5 hours at 10°C. and then for 12 hours at 20° C. After cooling again to 10° C., 9.97 g(98.70 mmol) of triethylamine, dissolved in 20 ml of NMP, are added tothe reaction mixture, which is warmed up to room temperature and stirredfor 2 hours.

[0142] In order to isolate the polymer, the reaction mixture is filteredand the filtrate is added dropwise to 1 500 ml of 2-propanol. Theprecipitated polymer is filtered off with suction and washed twice in 2000 ml portions of cold demineralized water and once in 1 000 ml ofdemineralized water at 80° C., filtered off, and dried for 72 hours at50° C./10 mbar. The yield is 21.52 g.

[0143] The polyhydroxyamide prepared in this manner is readily solublein solvents such as NMP, γ-BL, tetrahydrofuran, cyclohexanone,cyclopentanone and diethylene glycol monomethyl ether.

Example 7 Polyhydroxyamide 7

[0144] 7.00 g (32.40 mmol) of bisaminophenol 4 are dissolved in 100 mlof distilled NMP. A solution of 8.22 g (40.50 mmol) of dicarboxylic acidchloride 4 in 50 ml of distilled γ-BL is added dropwise to this solutionat 10° C. while stirring. Stirring is effected for a further hour at 10°C. and then for 1 hour at 20° C. A solution of 9.40 g (16.20 mmol) ofbishydroxyester 1 in 60 ml of distilled NMP is then added dropwise at10° C. The reaction solution is stirred for a further 1.5 hours at 10°C. and then for 12 hours at 20° C. After cooling again to 10° C., 10.20g (101.0 mmol) of triethylamine, dissolved in 20 ml of NMP, are added tothe reaction mixture, which is warmed up to room temperature and stirredfor 2 hours.

[0145] In order to isolate the polymer, the reaction mixture is filteredand the filtrate is added dropwise to 1 500 ml of 2-propanol. Theprecipitated polymer is filtered off with suction and washed twice in 2000 ml portions of cold demineralized water and once in 1 000 ml ofdemineralized water at 80° C., filtered off, and dried for 72 hours at50° C./10 mbar. The yield is 13.5 g.

[0146] The polyhydroxyamide prepared in this manner is readily solublein solvents such as NMP, γ-BL, tetrahydrofuran, cyclohexanone,cyclopentanone and diethylene glycol monomethyl ether.

Example 8 Polyhydroxyamide 8

[0147] 10 g (26.28 mmol) of bisaminophenol 4 are dissolved in 100 ml ofdistilled N-methylpyrrolidone (NMP). A solution of 9.56 g (31.54 mmol)of dicarboxylic acid chloride 1 in 50 ml of distilled γ-butyrolactone(γ-BL) is added dropwise to this solution at 10° C. while stirring.Stirring is effected for a further hour at 10° C. and then for 1 hour at20° C. A solution of 10.51 g (10.51 mmol) of bishydroxycarbonate 1 in 60ml of distilled NMP is then added dropwise at 10° C. The reactionsolution is stirred for a further 1.5 hours at 10° C. and then for 12hours at 20° C. After cooling again to 10° C., 7.96 g (78.5 mmol) oftriethylamine, dissolved in 20 ml of NMP, are added to the reactionmixture, which is warmed up to room temperature and stirred for 2 hours.

[0148] In order to isolate the polymer, the reaction mixture is filteredand the filtrate is added dropwise to 2 500 ml of 2-propanol. Theprecipitated polymer is filtered off with suction and washed twice in 1000 ml portions of cold demineralized water and once in 2 000 ml ofdemineralized water at 80° C., filtered off, and dried for 72 hours at50° C./10 mbar. The yield is 18.8 g. The polyhydroxyamide prepared inthis manner is readily soluble in solvents such as NMP, γ-BL,tetrahydrofuran, cyclohexanone, cyclopentanone and diethylene glycolmonomethyl ether.

Example 9 Polyhydroxyamide 9

[0149] 12.00 g (21.25 mmol) of bisaminophenol 1 are dissolved in 130 mlof distilled N-methylpyrrolidone (NMP). A solution of 3.55 g (15.66mmol) of dicarboxylic acid chloride 1 and 1.70 g (6.71 mmol) ofdicarboxylic acid chloride 8 (70:30) in 50 ml of distilledγ-butyrolactone (γ-BL) is added dropwise to this solution at 10° C.while stirring. Stirring is effected for a further hour at 10° C. andthen for 1 hour at 20° C. A solution of 11.50 g (5.75 mmol) ofbishydroxycarbonate 2 in 60 ml of distilled NMP is then added dropwiseat 10° C. The reaction solution is stirred for a further 1.5 hours at10° C. and then for 12 hours at 20° C. After cooling again to 10° C.,5.65 g (55.93 mmol) of triethylamine, dissolved in 20 ml of NMP, areadded to the reaction mixture, which is warmed up to room temperatureand stirred for 2 hours.

[0150] In order to isolate the polymer, the reaction mixture is filteredand the filtrate is added dropwise to 2 000 ml of 2-propanol. Theprecipitated polymer is filtered off with suction and washed twice in 1000 ml portions of cold demineralized water and once in 2 000 ml ofdemineralized water at 80° C., filtered off, and dried for 72 hours at50° C./10 mbar. The yield is 15.56 g. The polyhydroxyamide prepared inthis manner is readily soluble in solvents such as NMP, γ-BL,tetrahydrofuran, cyclohexanone, cyclopentanone and diethylene glycolmonomethyl ether.

[0151] Thermal, mechanical and adhesion properties (examples 10-30)

Example 10 Determination of the Thermal Stabilities

[0152] The polyhydroxyamides described have thermal stabilities of >450°C. according to TGA investigations (thermogravimetry, apparatus: STA1500 from Rheometric Scientific, heating rate: 5 K/min, inert gas:argon). The isothermal mass loss per hour at 400° C. for 10 hours is:

[0153] Example 1: 0.4%

[0154] Example 2: 0.2%

[0155] Example 3: 0.3%

[0156] Example 4: 0.3%

[0157] Example 5: 0.2%

[0158] Example 6: 0.3%

[0159] Example 7: 0.2%

[0160] Example 8: 0.3%

[0161] Example 9: 0.3%

[0162] The polyhydroxyamides 1-9 described thus meet the requirementsfor the intended applications.

Example 11 Preparation of a Polymer Solution of Polyhydroxyamide 1 andInvestigation of the Properties

[0163] 5 g of the polyhydroxyamide 1 described in example 1 aredissolved in 20 g of NMP (VLSI-Selectipur®). The dissolution process isexpediently effected on a shaking apparatus. The solution is thenfiltered under pressure through a 0.2 μm filter into a cleaned,particle-free sample tube.

a) Determination of the Adhesion of Polyhydroxyamide 1 to a TitaniumNitride Layer

[0164] A 4″ (10.16 cm) silicon wafer is provided with a 50 nm thicktitanium nitride layer by sputtering. The abovementioned solution isapplied to this wafer by spin coating, for 5 s at 500 rpm and for 25 sat 3 500 rpm. After a short softbake of 1 min at 120° C. on a hotplate,10 silicon chips measuring 4×4 mm², which were likewise provided on thesurface with 50 nm titanium nitride by sputtering, are pressed onto thepolyhydroxyamide 1 film with a force of 2 N. This stack is then heatedfor 1 h at 300° C. in a nitrogen atmosphere in an oven. After cooling toroom temperature, an adhesion test is carried out by means of a sheartester, Dage Series 400. The mean value of the force which was requiredfor shearing off the Si chips is 2.1 kg/mm² (20.60 N/mm²).

b) Determination of the Adhesion of Polyhydroxyamide 1 to a TantalumNitride Layer

[0165] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 5a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but oftantalum nitride. The mean value of the force which was required forshearing off the Si chips is 1.9 kg/mm² (18.64 N/mm²).

c) Determination of the Adhesion of Polyhydroxyamide 1 to a SiliconWafer

[0166] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 11a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but ofsilicon. The mean value of the force which was required for shearing offthe Si chips is 2.1 kg/mm² (20.60 N/mm²).

d) Determination of the Adhesion of Polyhydroxyamide 1 after ThermalLoading Tests

[0167] The same test specimens as in examples 11a-11c were producedagain. After heating at 300° C., this stack was subjected 50 times to athermal load in a conditioned cabinet, Vötsch VT7004, between −50° C.and 150° C. After this treatment, a shear test was carried out. Here,the forces were:

[0168] Example 11a: 1.9 kg/mm² (18.64 N/mm²)

[0169] Example 11b: 1.8 kg/mm² (17.66 N/mm²)

[0170] Example 11c: 2.0 kg/mm² (19.62 N/mm²)

Example 12 Preparation of a Polymer Solution of Polyhydroxyamide 2 andInvestigation of the Properties

[0171] 5 g of the polyhydroxyamide 2 described in example 2 aredissolved in 20 g of NMP (VLSI-Selectipur®). The dissolution process isexpediently effected on a shaking apparatus. The solution is thenfiltered under pressure through a 0.2 μm filter into a cleaned,particle-free sample tube.

a) Determination of the Adhesion of Polyhydroxyamide 2 to a TitaniumNitride Layer

[0172] A 4″ (10.16 cm) silicon wafer is provided with a 50 nm thicktitanium nitride layer by sputtering. The abovementioned solution isapplied to this wafer by spin coating, for 5 s at 500 rpm and for 25 sat 3 500 rpm. After a short softbake of 1 min at 120° C. on a hotplate,10 silicon chips measuring 4×4 mm², which were likewise provided on thesurface with 50 nm titanium nitride by sputtering, are pressed onto thepolyhydroxyamide 2 film with a force of 2 N. This stack is then heatedfor 1 h at 300° C. in a nitrogen atmosphere in an oven. After cooling toroom temperature, an adhesion test is carried out by means of a sheartester, Dage Series 400. The mean value of the force which was requiredfor shearing off the Si chips is 2.2 kg/mm² (21.58 N/mm²).

b) Determination of the Adhesion of Polyhydroxyamide 2 to a TantalumNitride Layer

[0173] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 12a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but oftantalum nitride. The mean value of the force which was required forshearing off the Si chips is 2.0 kg/mm² (19.62 N/mm²).

c) Determination of the Adhesion of Polyhydroxyamide 2 to a SiliconWafer

[0174] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 12a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but ofsilicon. The mean value of the force which was required for shearing offthe Si chips is 2.3 kg/mm² (22.56 N/mm²)

d) Determination of the Adhesion of Polyhydroxyamide 2 after ThermalLoading Tests

[0175] The same test specimens as in examples 12a to 12c were producedagain. After heating at 300° C., this stack was subjected 50 times to athermal load in a conditioned cabinet, Vötsch VT7004, between −50° C.and 150° C. After this treatment, a shear test was carried out. Here,the forces were:

[0176] Example 12a: 2.1 kg/mm² (20.60 N/mm²)

[0177] Example 12b: 1.9 kg/mm² (18.64 N/mm²)

[0178] Example 12c: 2.0 kg/mm² (19.62 N/mm²)

Example 13 Preparation of a Polymer Solution of Polyhydroxyamide 3 andInvestigation of the Properties

[0179] 5 g of the polyhydroxyamide 3 described in example 3 aredissolved in 20 g of NMP (VLSI-Selectipur®). The dissolution process isexpediently effected on a shaking apparatus. The solution is thenfiltered under pressure through a 0.2 μm filter into a cleaned,particle-free sample tube.

[0180] a) Determination of the Adhesion of Polyhydroxyamide 3 to aTitanium Nitride Layer

[0181] A 4″ (10.16 cm) silicon wafer is provided with a 50 nm thicktitanium nitride layer by sputtering. The abovementioned solution isapplied to this wafer by spin coating, for 5 s at 500 rpm and for 25 sat 3 500 rpm. After a short softbake of 1 min at 120° C. on a hotplate,10 silicon chips measuring 4×4 mm², which were likewise provided on thesurface with 50 nm titanium nitride by sputtering, are pressed onto thepolyhydroxyamide 3 film with a force of 2 N. This stack is then heatedfor 1 h at 300° C. in a nitrogen atmosphere in an oven. After cooling toroom temperature, an adhesion test is carried out by means of a sheartester, Dage Series 400. The mean value of the force which was requiredfor shearing off the Si chips is 1.9 kg/mm² (18.64 N/mm²).

b) Determination of the Adhesion of Polyhydroxyamide 3 to a TantalumNitride Layer

[0182] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 13a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but oftantalum nitride. The mean value of the force which was required forshearing off the Si chips is 1.8 kg/mm² (17.66 N/mm²).

c) Determination of the Adhesion of Polyhydroxyamide 3 to a SiliconWafer

[0183] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 13a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but ofsilicon. The mean value of the force which was required for shearing offthe Si chips is 2.0 kg/mm² (19.62 N/mm²).

d) Determination of the Adhesion of Polyhydroxyamide 3 after ThermalLoading Tests

[0184] The same test specimens as in examples 13a to 13c were producedagain. After heating at 300° C., this stack was subjected 50 times to athermal load in a conditioned cabinet, Vötsch VT7004, between −50° C.and 150° C. After this treatment, a shear test was carried out. Here,the forces were:

[0185] Example 13a: 1.7 kg/mm² (16.67 N/mm²)

[0186] Example 13b: 1.7 kg/mm² (16.67 N/mm²)

[0187] Example 13c: 1.8 kg/mm² (17.66 N/mm²)

Example 14 Preparation of a Polymer Solution of Polyhydroxyamide 4 andInvestigation of the Properties

[0188] 5 g of the polyhydroxyamide 4 described in example 4 aredissolved in 20 g of NMP (VLSI-Selectipur®). The dissolution process isexpediently effected on a shaking apparatus. The solution is thenfiltered under pressure through a 0.2 μm filter into a cleaned,particle-free sample tube.

a) Determination of the Adhesion of Polyhydroxyamide 4 to a TitaniumNitride Layer

[0189] A 4″ (10.16 cm) silicon wafer is provided with a 50 nm thicktitanium nitride layer by sputtering. The abovementioned solution isapplied to this wafer by spin coating, for 5 s at 500 rpm and for 25 sat 3 500 rpm. After a short softbake of 1 min at 120° C. on a hotplate,10 silicon chips measuring 4×4 mm², which were likewise provided on thesurface with 50 nm titanium nitride by sputtering, are pressed onto thepolyhydroxyamide 4 film with a force of 2 N. This stack is then heatedfor 1 h at 300° C. in a nitrogen atmosphere in an oven. After cooling toroom temperature, an adhesion test is carried out by means of a sheartester, Dage Series 400. The mean value of the force which was requiredfor shearing off the Si chips is 2.0 kg/mm² (19.62 N/mm²).

b) Determination of the Adhesion of Polyhydroxyamide 4 to a TantalumNitride Layer

[0190] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 14a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but oftantalum nitride. The mean value of the force which was required forshearing off the Si chips is 1.9 kg/mm² (18.64 N/mm²).

c) Determination of the Adhesion of Polyhydroxyamide 4 to a SiliconWafer

[0191] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 14a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but ofsilicon. The mean value of the force which was required for shearing offthe Si chips is 2.1 kg/mm² (20.60 N/mm²).

d) Determination of the Adhesion of Polyhydroxyamide 4 after ThermalLoading Tests

[0192] The same test specimens as in examples 14a to 14c were producedagain. After heating at 300° C., this stack was subjected 50 times to athermal load in a conditioned cabinet, Vötsch VT7004, between −50° C.and 150° C. After this treatment, a shear test was carried out. Here,the forces were:

[0193] Example 14a: 1.8 kg/mm² (17.66 N/mm²)

[0194] Example 14b: 1.75 kg/mm² (17.17 N/mm²)

[0195] Example 14c: 2.0 kg/mm² (19.62 N/mm²)

Example 15 Preparation of a Polymer Solution of Polyhydroxyamide 5 andInvestigation of the Properties

[0196] 5 g of the polyhydroxyamide 5 described in example 5 aredissolved in 20 g of NMP (VLSI-Selectipur®). The dissolution process isexpediently effected on a shaking apparatus. The solution is thenfiltered under pressure through a 0.2 μm filter into a cleaned,particle-free sample tube.

a) Determination of the Adhesion of Polyhydroxyamide 5 to a TitaniumNitride Layer

[0197] A 4″ (10.16 cm) silicon wafer is provided with a 50 nm thicktitanium nitride layer by sputtering. The abovementioned solution isapplied to this wafer by spin coating, for 5 s at 500 rpm and for 25 sat 3 500 rpm. After a short softbake of 1 min at 120° C. on a hotplate,10 silicon chips measuring 4×4 mm², which were likewise provided on thesurface with 50 nm titanium nitride by sputtering, are pressed onto thepolyhydroxyamide 5 film with a force of 2 N. This stack is then heatedfor 1 h at 300° C. in a nitrogen atmosphere in an oven. After cooling toroom temperature, an adhesion test is carried out by means of a sheartester, Dage Series 400. The mean value of the force which was requiredfor shearing off the Si chips is 2.2 kg/mm² (21.58 N/mm²).

b) Determination of the Adhesion of Polyhydroxyamide 5 to a TantalumNitride Layer

[0198] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 15a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but oftantalum nitride. The mean value of the force which was required forshearing off the Si chips is 2.0 kg/mm² (19.62 N/mm²).

c) Determination of the Adhesion of Polyhydroxyamide 5 to a SiliconWafer

[0199] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 15a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but ofsilicon. The mean value of the force which was required for shearing offthe Si chips is 2.3 kg/mm² (22.56 N/mm²)

d) Determination of the Adhesion of Polyhydroxyamide 5 after ThermalLoading Tests

[0200] The same test specimens as in examples 15a to 15c were producedagain. After heating at 300° C., this stack was subjected 50 times to athermal load in a conditioned cabinet, Vötsch VT7004, between −50° C.and 150° C. After this treatment, a shear test was carried out. Here,the forces were:

[0201] Example 15a: 2.1 kg/mm² (20.60 N/mm²)

[0202] Example 15b: 1.9 kg/mm² (18.64 N/mm²)

[0203] Example 15c: 2.0 kg/mm² (19.62 N/mm²)

Example 16 Preparation of a Polymer Solution of Polyhydroxyamide 6 andInvestigation of the Properties

[0204] 15 g of the polyhydroxyamide 6 described in example 6 aredissolved in 20 g of NMP (VLSI-Selectipur®). The dissolution process isexpediently effected on a shaking apparatus. The solution is thenfiltered under pressure through a 0.2 μm filter into a cleaned,particle-free sample tube.

a) Determination of the Adhesion of Polyhydroxyamide 6 to a TitaniumNitride Layer

[0205] A 4″ (10.16 cm) silicon wafer is provided with a 50 nm thicktitanium nitride layer by sputtering. The abovementioned solution isapplied to this wafer by spin coating, for 5 s at 500 rpm and for 25 sat 3 500 rpm. After a short softbake of 1 min at 120° C. on a hotplate,10 silicon chips measuring 4×4 mm², which were likewise provided on thesurface with 50 nm titanium nitride by sputtering, are pressed onto thepolyhydroxyamide 6 film with a force of 2 N. This stack is then heatedfor 1 h at 300° C. in a nitrogen atmosphere in an oven. After cooling toroom temperature, an adhesion test is carried out by means of a sheartester, Dage Series 400. The mean value of the force which was requiredfor shearing off the Si chips is 1.9 kg/mm² (18.64 N/mm²).

b) Determination of the Adhesion of Polyhydroxyamide 6 to a TantalumNitride Layer

[0206] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 16a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but oftantalum nitride. The mean value of the force which was required forshearing off the Si chips is 1.9 kg/mm² (18.64 N/mm²).

c) Determination of the Adhesion of Polyhydroxyamide 6 to a SiliconWafer

[0207] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 16a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but ofsilicon. The mean value of the force which was required for shearing offthe Si chips is 1.8 kg/mm² (17.66 N/mm²).

d) Determination of the Adhesion of Polyhydroxyamide 6 after ThermalLoading Tests

[0208] The same test specimens as in examples 16a to 16c were producedagain. After heating at 300° C., this stack was subjected 50 times to athermal load in a conditioned cabinet, Vötsch VT7004, between −50° C.and 150° C. After this treatment, a shear test was carried out. Here,the forces were:

[0209] Example 16a: 1.8 kg/mm² (17.66 N/mm²)

[0210] Example 16b: 1.7 kg/mm² (16.67 N/mm²)

[0211] Example 16c: 1.6 kg/mm² (15.69 N/mm²)

Example 17 Preparation of a Polymer Solution of Polyhydroxyamide 7 andInvestigation of the Properties

[0212] 5 g of the polyhydroxyamide 7 described in example 7 aredissolved in 20 g of NMP (VLSI-Selectipur®). The dissolution process isexpediently effected on a shaking apparatus. The solution is thenfiltered under pressure through a 0.2 μm filter into a cleaned,particle-free sample tube.

a) Determination of the Adhesion of Polyhydroxyamide 7 to a TitaniumNitride Layer

[0213] A 4″ (10.16 cm) silicon wafer is provided with a 50 nm thicktitanium nitride layer by sputtering. The abovementioned solution isapplied to this wafer by spin coating, for 5 s at 500 rpm and for 25 sat 3 500 rpm. After a short softbake of 1 min at 120° C. on a hotplate,10 silicon chips measuring 4×4 mm², which were likewise provided on thesurface with 50 nm titanium nitride by sputtering, are pressed onto thepolyhydroxyamide 4 film with a force of 2 N. This stack is then heatedfor 1 h at 300° C. in a nitrogen atmosphere in an oven. After cooling toroom temperature, an adhesion test is carried out by means of a sheartester, Dage Series 400. The mean value of the force which was requiredfor shearing off the Si chips is 2.2 kg/mm² (21.58 N/mm²).

b) Determination of the Adhesion of Polyhydroxyamide 7 to a TantalumNitride Layer

[0214] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 17a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but oftantalum nitride. The mean value of the force which was required forshearing off the Si chips is 2.2 kg/mm² (21.58 N/mm²)

c) Determination of the Adhesion of Polyhydroxyamide 7 to a SiliconWafer

[0215] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 17a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but ofsilicon. The mean value of the force which was required for shearing offthe Si chips is 2.1 kg/mm² (20.60 N/mm²).

d) Determination of the Adhesion of Polyhydroxyamide 7 after ThermalLoading Tests

[0216] The same test specimens as in examples 17a to 17c were producedagain. After heating at 300° C., this stack was subjected 50 times to athermal load in a conditioned cabinet, Vötsch VT7004, between −50° C.and 150° C. After this treatment, a shear test was carried out. Here,the forces were:

[0217] Example 17a: 2.1 kg/mm² (20.60 N/mm²)

[0218] Example 17b: 2.15 kg/mm² (21.09 N/mm²)

[0219] Example 17c: 2.0 kg/mm² (19.62 N/mm²)

Example 18 Preparation of a Polymer Solution of Polyhydroxyamide 8 andInvestigation of the Properties

[0220] 5 g of the polyhydroxyamide 8 described in example 8 aredissolved in 20 g of NMP (VLSI-Selectipur®). The dissolution process isexpediently effected on a shaking apparatus. The solution is thenfiltered under pressure through a 0.2 μm filter into a cleaned,particle-free sample tube.

a) Determination of the Adhesion of Polyhydroxyamide 8 to a TitaniumNitride Layer

[0221] A 4″ (10.16 cm) silicon wafer is provided with a 50 nm thicktitanium nitride layer by sputtering. The abovementioned solution isapplied to this wafer by spin coating, for 5 s at 500 rpm and for 25 sat 3 500 rpm. After a short softbake of 1 min at 120° C. on a hotplate,10 silicon chips measuring 4×4 mm², which were likewise provided on thesurface with 50 nm titanium nitride by sputtering, are pressed onto thepolyhydroxyamide 5 film with a force of 2 N. This stack is then heatedfor 1 h at 300° C. in a nitrogen atmosphere in an oven. After cooling toroom temperature, an adhesion test is carried out by means of a sheartester, Dage Series 400. The mean value of the force which was requiredfor shearing off the Si chips is 2.2 kg/mm² (21.58 N/mm²).

b) Determination of the Adhesion of Polyhydroxyamide 8 to a TantalumNitride Layer

[0222] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 18a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but oftantalum nitride. The mean value of the force which was required forshearing off the Si chips is 1.9 kg/mm² (18.64 N/mm²)

c) Determination of the Adhesion of Polyhydroxyamide 8 to a SiliconWafer

[0223] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 18a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but ofsilicon. The mean value of the force which was required for shearing offthe Si chips is 2.3 kg/mm² (22.56 N/mm²).

d) Determination of the Adhesion of Polyhydroxyamide 8 after ThermalLoading Tests

[0224] The same test specimens as in examples 18a to 18c were producedagain. After heating at 300° C., this stack was subjected 50 times to athermal load in a conditioned cabinet, Vötsch VT7004, between −50° C.and 150° C. After this treatment, a shear test was carried out. Here,the forces were:

[0225] Example 18a: 2.1 kg/mm² (20.60 N/mm²)

[0226] Example 18b: 1.8 kg/mm² (17.66 N/mm²)

[0227] Example 18c: 2.0 kg/mm² (19.62 N/mm²)

Example 19 Preparation of a Polymer Solution of Polyhydroxyamide 9 andInvestigation of the Properties

[0228] 5 g of the polyhydroxyamide 9 described in example 9 aredissolved in 20 g of NMP (VLSI-Selectipur®). The dissolution process isexpediently effected on a shaking apparatus. The solution is thenfiltered under pressure through a 0.2 μm filter into a cleaned,particle-free sample tube.

a) Determination of the Adhesion of Polyhydroxyamide 9 to a TitaniumNitride Layer

[0229] A 4″ (10.16 cm) silicon wafer is provided with a 50 nm thicktitanium nitride layer by sputtering. The abovementioned solution isapplied to this wafer by spin coating, for 5 s at 500 rpm and for 25 sat 3 500 rpm. After a short softbake of 1 min at 120° C. on a hotplate,10 silicon chips measuring 4×4 mm², which were likewise provided on thesurface with 50 nm titanium nitride by sputtering, are pressed onto thepolyhydroxyamide 6 film with a force of 2 N. This stack is then heatedfor 1 h at 300° C. in a nitrogen atmosphere in an oven. After cooling toroom temperature, an adhesion test is carried out by means of a sheartester, Dage Series 400. The mean value of the force which was requiredfor shearing off the Si chips is 1.9 kg/mm² (18.64 N/mm²)

b) Determination of the Adhesion of Polyhydroxyamide 9 to a TantalumNitride Layer

[0230] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 19a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but oftantalum nitride. The mean value of the force which was required forshearing off the Si chips is 1.9 kg/mm² (18.64 N/mm²).

c) Determination of the Adhesion of Polyhydroxyamide 9 to a SiliconWafer

[0231] The experiment was carried out in exactly the same way as withtitanium nitride (cf. example 19a), except that in this case the surfaceof the wafer and of the chips consisted not of titanium nitride but ofsilicon. The mean value of the force which was required for shearing offthe Si chips is 1.8 kg/mm² (17.66 N/mm²)

d) Determination of the Adhesion of Polyhydroxyamide 9 after ThermalLoading Tests

[0232] The same test specimens as in examples 19a to 19c were producedagain. After heating at 300° C., this stack was subjected 50 times to athermal load in a conditioned cabinet, Vötsch VT7004, between −50° C.and 150° C. After this treatment, a shear test was carried out. Here,the forces were:

[0233] Example 19a: 1.8 kg/mm² (17.66 N/mm²)

[0234] Example 19b: 1.7 kg/mm² (16.67 N/mm²)

[0235] Example 19c: 1.7 kg/mm² (16.67 N/mm²)

Example 20 Comparative Example for Adhesion

[0236] A polyhydroxyamide prepared analogously to example 1 of U.S. Pat.No. 5,077,378 and in the same solution in NMP as in example 11 and thesame experiments as in 11a to 11c gave the following mean values:Titanium surface:  1.5 kg/mm² (14.71 N/mm²) Tantalum nitride surface: 1.6 kg/mm² (15.69 N/mm²) Silicon surface: 1.55 kg/mm² (15.21 N/mm²)

Example 21 Determination of the Resilience of Polyhydroxyamide 1

[0237] For the polyhydroxyamide 1 described under example 1,substantially higher resiliences were determined compared with thematerial in example 1 of U.S. Pat. No. 5,077,378. Tensile test [sic]were carried out using the apparatus MTS 858 from MTS System Corp. onfilms. The elongation is 82%. After the load is removed, the materialcontracts completely.

Example 22 Determination of the Resilience of Polyhydroxyamide 2

[0238] Tensile test [sic] were carried out using the apparatus MTS 858from MTS System Corp. on films. The elongation is 62%. After the load isremoved, the material contracts completely.

Example 23 Determination of the Resilience of Polyhydroxyamide 3

[0239] Tensile test [sic] were carried out using the apparatus MTS 858from MTS System Corp. on films. The elongation is 78%. After the load isremoved, the material contracts completely.

Example 24 Determination of the Resilience of Polyhydroxyamide 4

[0240] Tensile test [sic] were carried out using the apparatus MTS 858from MTS System Corp. on films. The elongation is 80%. After the load isremoved, the material contracts completely.

Example 25 Determination of the Resilience of Polyhydroxyamide 5

[0241] Tensile test [sic] were carried out using the apparatus MTS 858from MTS System Corp. on films. The elongation is 62%. After the load isremoved, the material contracts completely.

Example 26 Determination of the Resilience of Polyhydroxyamide 6

[0242] Tensile test [sic] were carried out using the apparatus MTS 858from MTS System Corp. on films. The elongation is 76%. After the load isremoved, the material contracts completely.

Example 27 Determination of the Resilience of Polyhydroxyamide 7

[0243] Tensile test [sic] were carried out using the apparatus MTS 858from MTS System Corp. on films. The elongation is 83%. After the load isremoved, the material contracts completely.

Example 28 Determination of the Resilience of Polyhydroxyamide 8

[0244] Tensile test [sic] were carried out using the apparatus MTS 858from MTS System Corp. on films. The elongation is 75%. After the load isremoved, the material contracts completely.

Example 29 Determination of the Resilience of Polyhydroxyamide 9

[0245] Tensile test [sic] were carried out using the apparatus MTS 858from MTS System Corp. on films. The elongation is 70%. After the load isremoved, the material contracts completely.

Example 30 Comparative Example for Resilience

[0246] A polyhydroxyamide prepared analogously to example 1 of U.S. Pat.No. 5,077,378 was subjected to a tensile test using the apparatus MTS858 from MTS System Corp. on films. The elongation is 9%.

FURTHER SYNTHESIS EXAMPLES Example 31 Polyhydroxyamide 10

[0247] 7.78 g (21.25 mmol) of bisaminophenol 2 are dissolved in 130 mlof distilled N-methylpyrrolidone (NMP). A solution of 4.62 g (15.66mmol) of dicarboxylic acid chloride 2 and 2.03 g (6.71 mmol) ofdicarboxylic acid chloride 5 (70:30) in 50 ml of distilledγ-butyrolactone (γ-BL) is added dropwise to this solution at 10° C.while stirring. Stirring is effected for a further hour at 10° C. andthen for 1 hour at 20° C. A solution of 5.75 g (5.75 mmol) ofbishydroxycarbonate 1 in 60 ml of distilled NMP is then added dropwiseat 10° C. The reaction solution is stirred for a further 1.5 hours at10° C. and then for 12 hours at 20° C. After cooling again to 10° C.,5.65 g (55.93 mmol) of triethylamine, dissolved in 20 ml of NMP, areadded to the reaction mixture, which is warmed up to room temperatureand stirred for 2 hours. In order to isolate the polymer, the reactionmixture is filtered and the filtrate is added dropwise to 2 000 ml of2-propanol. The precipitated polymer is filtered off with suction andwashed twice in 1 000 ml portions of cold demineralized water and oncein 2 000 ml of demineralized water at 80° C., filtered off, and driedfor 72 hours at 50° C./10 mbar. The yield is 14.86 g. Thepolyhydroxyamide prepared in this manner is readily soluble in solventssuch as NMP, γ-BL, tetrahydrofuran, cyclohexanone, cyclopentanone anddiethylene glycol monomethyl ether.

Example 32 Polyhydroxyamide 11

[0248] 7.78 g (17 mmol) of bisaminophenol 1 and 1.55 g (4.24 mmol) ofbisaminophenol 2 are dissolved in 140 ml of distilledN-methylpyrrolidone (NMP). A solution of 5.08 g (22.37 mmol) ofdicarboxylic acid chloride 1 in 70 ml of distilled γ-butyrolactone(γ-BL) is added dropwise to this solution at 10° C. while stirring.Stirring is effected for a further hour at 10° C. and then for 1 hour at20° C. A solution of 11.50 g (5.75 mmol) of bishydroxycarbonate 2 in 60ml of distilled NMP is then added dropwise at 10° C. The reactionsolution is stirred for a further 1.5 hours at 10° C. and then for 12hours at 20° C. After cooling again to 10° C., 5.65 g (55.93 mmol) oftriethylamine, dissolved in 20 ml of NMP, are added to the reactionmixture, which is warmed up to room temperature and stirred for 2 hours.In order to isolate the polymer, the reaction mixture is filtered andthe filtrate is added dropwise to 2 000 ml of 2-propanol. Theprecipitated polymer is filtered off with suction and washed twice in 1000 ml portions of cold demineralized water and once in 2 000 ml ofdemineralized water at 80° C., filtered off, and dried for 72 hours at50° C./10 mbar. The yield is 16.19 g. The polyhydroxyamide prepared inthis manner is readily soluble in solvents such as NMP, γ-BL,tetrahydrofuran, cyclohexanone, cyclopentanone and diethylene glycolmonomethyl ether.

Example 33 Polyhydroxyamide 12

[0249] 172.14 g (0.47 mol) of bisaminophenol 2 are dissolved in 600 mlof distilled NMP. A solution of 97.45 g (0.48 mol) of dicarboxylic acidchloride 3 in 550 ml of distilled γ-BL is added dropwise to thissolution at 10° C. while stirring. Stirring is effected for a furtherhour at 10° C. and then for 1 hour at 20° C. A solution of 240 g (0.12mol) of bishydroxycarbonate 2 in 500 ml of distilled γ-BL is then addeddropwise at 10° C. The reaction solution is stirred for a further 1.5hours at 10° C. and then for 12 hours at 20° C. A solution of 19.7 g(0.12 mol) of endcap 1 in 150 ml of distilled γ-BL is then addeddropwise at 10° C. The reaction solution is stirred for a further 1.5hours at 10° C. and then for 12 hours at 20° C. After cooling again to10° C., 129.4 g (1.6 mol) of pyridine, dissolved in 450 ml of γ-BL, areadded to the reaction mixture, which is warmed up to room temperatureand stirred for 2 hours.

[0250] In order to isolate the polymer, the reaction mixture is filteredand the filtrate is added dropwise to a mixture of 3 500 ml ofdemineralized water and 1 500 ml of 2-propanol. The precipitated polymeris filtered off with suction and washed twice in 2 000 ml portions ofcold demineralized water and once in 1 000 ml of demineralized water at80° C., filtered off, and dried for 72 hours at 50° C./10 mbar. Theyield is 459.3 g.

[0251] The polyhydroxyamide prepared in this manner is readily solublein solvents such as NMP, γ-BL, tetrahydrofuran, cyclohexanone,cyclopentanone and diethylene glycol monomethyl ether. It has terminalgroups introduced by endcap 1. The product can be completely cyclized togive the corresponding polybenzoxazole.

Example 34 Polyhydroxyamide 13

[0252] 135.51 g (0.24 mol) of bisaminophenol 1 and 51.89 g (0.24 mol) ofbisaminophenol 3 are dissolved in 600 ml of distilled NMP. A solution of56.76 g (0.25 mol) of dicarboxylic acid chloride 1 and 50.75 g (0.25mol) of dicarboxylic acid chloride 3 in 550 ml of distilled γ-BL isadded dropwise to this solution at 10° C. while stirring. Stirring iseffected for a further hour at 10° C. and then for 1 hour at 20° C. Asolution of 120 g (0.12 mol) of bishydroxycarbonate 1 in 400 ml ofdistilled γ-BL is then added dropwise at 10° C. The reaction solution isstirred for a further 1.5 hours at 10° C. and then for 12 hours at 20°C. A solution of 12.54 g (0.12 mol) of endcap 2 in 120 ml of distilledγ-BL is then added dropwise at 10° C. The reaction solution is stirredfor a further 1.5 hours at 10° C. and then for 12 hours at 20° C. Aftercooling again to 10° C., 129.4 g (1.6 mol) of pyridine, dissolved in 450ml of γ-BL, are added to the reaction mixture, which is warmed up toroom temperature and stirred for 2 hours.

[0253] In order to isolate the polymer, the reaction mixture is filteredand the filtrate is added dropwise to a mixture of 3 000 ml ofdemineralized water and 1 000 ml of 2-propanol. The precipitated polymeris filtered off with suction and washed twice in 2 000 ml portions ofcold demineralized water and once in 1 000 ml of demineralized water at80° C., filtered off, and dried for 72 hours at 50° C./10 mbar. Theyield is 393.7 g.

[0254] The polyhydroxyamide prepared in this manner is readily solublein solvents such as NMP, γ-BL, tetrahydrofuran, cyclohexanone,cyclopentanone and diethylene glycol monomethyl ether.

Example 35 Polyhydroxyamide 14

[0255] 172.14 g (0.47 mol) of bisaminophenol 2 are dissolved in 600 mlof distilled NMP. A solution of 97.45 g (0.48 mol) of dicarboxylic acidchloride 3 in 550 ml of distilled γ-BL is added dropwise to thissolution at 10° C. while stirring. Stirring is effected for a furtherhour at 10° C. and then for 1 hour at 20° C. A solution of 300 g (0.12mol) of polyether 1 in 500 ml of distilled γ-BL is then added dropwiseat 10° C. The reaction solution is stirred for a further 1.5 hours at10° C. and then for 12 hours at 20° C. A solution of 19.7 g (0.12 mol)of endcap 1 in 150 ml of distilled γ-BL is then added dropwise at 10° C.The reaction solution is stirred for a further 1.5 hours at 10° C. andthen for 12 hours at 20° C. After cooling again to 10° C., 129.4 g (1.6mol) of pyridine, dissolved in 450 ml of γ-BL, are added to the reactionmixture, which is warmed up to room temperature and stirred for 2 hours.

[0256] In order to isolate the polymer, the reaction mixture is filteredand the filtrate is added dropwise to a mixture of 3 500 ml ofdemineralized water and 1 500 ml of 2-propanol. The precipitated polymeris filtered off with suction and washed twice in 2 000 ml portions ofcold demineralized water and once in 1 000 ml of demineralized water at80° C., filtered off, and dried for 72 hours at 50° C./10 mbar. Theyield is 463.5 g. The polyhydroxyamide prepared in this manner isreadily soluble in solvents such as NMP, γ-BL, tetrahydrofuran,cyclohexanone, cyclopentanone and diethylene glycol monomethyl ether.Thermal load capacity and resilience and adhesion on various substrateswere outstanding.

[0257] Thermal load capacity, resilience and adhesion on varioussubstrates were also outstanding for the polyhydroxyamides 10 to 13.

1. A polyhydroxyamide of the following formula I or formula II:

in which: a=0 or 1, with the proviso that, if a is 0, c must be ≧1,b=0-100, c=0-50, with the proviso that, if c is 0, a must be 1, d=1-100,e=0-100, f=0-100, g=0-50, h=0-100, k=0-100, m=0-100, n=0-50, p=0 or 1;

in which: q=1-100, r=1-100, s=0-100, t=0-100, u=0-100, v=0-50, w=0-100,x=0-100, y=0-100, z=0-50; X, independently of one another, are:

in which R₁ in each case may be identical to or different from R₂, andα=0-100 and β=0-100, α and β not simultaneously being 0; R₁ and R₂ are:substituted or unsubstituted alkylene, arylene or cycloalkylene groups;Q is —O—, —S— and/or —NH—; A₁ and/or A₂, where A₁ may be identical to ordifferent from A₂ if A₁ and/or A₂ are bonded to Q or —NH—, are: H,substituted or unsubstituted alkylcarbonyl, alkenylcarbonyl,cycloalkenylcarbonyl, arylcarbonyl, aralkylcarbonyl, aralkenylcarbonylor aralkynylcarbonyl, it being possible for the carbonyl group to bebonded to the aromatic or to the alkyl or alkenyl or alkynyl group; A₁and/or A₂, where A₁ may be identical to or different from A₂ if A₁and/or A₂ are bonded to —CO—, are: hydroxyl, substituted orunsubstituted alkoxy, alkenyloxy, aryloxy, cycloalkenyloxy, amino,alkylamino, alkenylamino, arylamino, arylalkenyloxy, arylalkylamino; A₃is: H, substituted or unsubstituted alkylcarbonyl, alkenylcarbonyl,cycloalkenylcarbonyl, arylcarbonyl, aralkylcarbonyl, aralkenylcarbonylor aralkynylcarbonyl, it being possible for the carbonyl group to bebonded to the aromatic or to the alkyl or alkenyl or alkynyl group; Y₁and Y₂, where Y₁ may be identical to or different from Y₂, are:substituted or unsubstituted aryl, a substituted or unsubstitutedpolynuclear aromatic hydrocarbon compound, substituted or unsubstitutedalkyl, alkenyl, alkynyl, aryl or aralkyl, aralkenyl, aralkynyl; Z₁ andZ₂, where Z₁ may be identical to or different from Z₂, are: aryl,aralkyl, aralkenyl, aralkynyl, heteroaryl or a polynuclear aromatichydrocarbon compound.
 2. The polyhydroxyamide as claimed in claim 1,characterized in that, in formula I, b=0-20, c=0-10, d=4-40, e=0-20,f=0-20, g=0-10, h=0-20, k=0-20, m=0-20 and/or n=0-10; and, in formulaII, q=3-40, r=1-40, s=0-40, t=0-20, u=0-20, v=0-10, w=0-20, x=0-20,y=0-20 and/or z=0-10.
 3. The polyhydroxyamide as claimed in claim 1 or2, characterized in that, in X, α=0-10 and/or β=0-10.
 4. Thepolyhydroxyamide as claimed in one or more of the preceding claims,characterized in that R₁ and/or R₂ have the following meaning: —(CH₂)₁₀₂—χ=1-20

where δ=0-20, ε=0-20, and R₃ and R₄: —H, —(CH₂)_(φ)—CH₃; φ=0-10 or —OH,and R₃ and R₄ cannot simultaneously be —OH


5. The polyhydroxyamide as claimed in one or more of the precedingclaims, characterized in that Q is —O— and/or —NH—.
 6. Thepolyhydroxyamide as claimed in one or more of the preceding claims,characterized in that A₁ and/or A₂, if A₁ and/or A₂ are bonded to Q or—NH—, and A₃ have the following meaning:

in which φ=0-10 and W=—CN, —C(CH₃)₃, —(CH₂)_(φ)—CH₃, —(CF₂)_(φ)—CF₃,—O—(CH₂)₁₀₀ —CH₃, —O—(CF₂)_(φ)—CF₃, —CH═CH₂, —C≡CH or


7. The polyhydroxyamide as claimed in one or more of the precedingclaims, characterized in that, if A₁ and/or A₂ are bonded to —CO—, A₁and/or A₂ have the following meaning:

in which φ=0-10 and W=—CN, —C(CH₃)₃, —(CH₂)_(φ)—CH₃, —(CF₂)_(φ)—CF₃,—O—(CH₂)_(φ)—CH₃, —O—(CF₂)_(φ)—CF₃, —CH═CH₂, —C≡CH or


8. The polyhydroxyamide as claimed in one or more of the precedingclaims, characterized in that Y₁ and Y₂ have the following meaning, itbeing possible for Y₁ to be identical to or different from Y₂:

—(CH₂)_(γ)—R₆—(CH₂)_(γ)—(γ=1-10) if R₆=—CH₂—, then γ=0-10
 9. Thepolyhydroxyamide as claimed in one or more of the preceding claims,characterized in that R₅ is —H, —CN, —C (CH₃)₃, —(CH₂)_(φ)—CH₃,—(CF₂)_(φ)—CF₃, —O—(CH₂)_(φ)—CH₃, —O—(CF₂)_(φ)—CF₃ and/or is:

in which φ=0-10 and W=—CN—, —C(CH₃)₃, —(CH₂)_(φ)—CH₃, —(CF₂)_(φ)—CF₃,—O—(CH₂)_(φ)—CH₃, —O—(CF₂)_(φ)—CF₃, —CH═CH₂, —C≡CH or


10. The polyhydroxyamide as claimed in one or more of the precedingclaims, characterized in that R₆ is —O—, —CO—, —NR₇—, —S—, —SO₂—, —S₂—,—CH₂— and/or is: —C═C— —C≡C—


11. The polyhydroxyamide as claimed in one or more of the precedingclaims, characterized in that R₇ is —H and/or is:


12. The polyhydroxyamide as claimed in one or more of the precedingclaims, characterized in that R₈ is an alkyl radical having 1 to 10carbon atoms or an aryl radical.
 13. The polyhydroxyamide as claimed inone or more of the preceding claims, characterized in that Z₁ and Z₂,where Z₁ may be identical to or different from Z₂, are:


14. A polybenzoxazole, characterized in that it was obtained bycyclization of hydroxyamide units of a polyhydroxyamide as claimed inone or more of the preceding claims.
 15. An electronic component whichhas a coat of a polybenzoxazole as claimed in claim
 14. 16. Theelectronic component as claimed in claim 15, characterized in that it isa memory chip, logic chip, flip chip, flash memory, multichip module,circuit board, microprocessor or embedded DRAM.
 17. A process for thepreparation of polyhydroxyamides as claimed in one or more of claims1-13, characterized in that a compound of the formula Z₁(NH₂)₂(OH)₂and/or Z₂(NH₂)₂(OH)₂ is reacted with a compound of the formula Y₁(COCl)₂and/or Y₂(COCl)₂, the product obtained is then reacted with a compoundof the formula X(QOH)₂ or X(QNH₂)₂, and then optionally the productobtained is reacted with a precursor compound for formula A₁, A₂ and/orA₃, Z₁, Z₂, Y₁, Y₂, A₁, A₂, A₃ and X being defined as in claims 1-13.18. A process for the preparation of polybenzoxazoles, characterized inthat polyhydroxyamides as claimed in one or more of claims 1-13 aresubjected to a thermal treatment.
 19. The process as claimed in claim18, characterized in that the thermal treatment is effected at 250-450°C., preferably at 300-400° C., most preferably at 300-350° C.
 20. Theprocess as claimed in claim 18 or 19, characterized in that the thermaltreatment is effected for 0.5-3 hours, preferably 1-3 hours, mostpreferably 1-2 hours.
 21. A process for coating substrates,characterized in that polyhydroxyamides as claimed in one or more ofclaims 1-13 are applied to the substrate to be coated, and the coatedsubstrate is then heated in order to form a polybenzoxazole coat on thesubstrate.
 22. The process as claimed in claim 21, characterized in thatthe polyhydroxyamides are dissolved in an organic solvent beforeapplication to the substrate.
 23. The process as claimed in claim 22,characterized in that the organic solvent is acetone, cyclohexanone,diethylene glycol monoethyl ether, diethylene glycol diethyl ether,N-methylpyrrolidone, γ-butyrolactone, ethyl lactate, tetrahydrofuran,methyl acetate or a mixture thereof.
 24. The process as claimed in claim21, 22 or 23, characterized in that the polyhydroxyamide is applied tothe substrate and a spin-coating treatment is then carried out.
 25. Theprocess as claimed in one or more of claims 21-24, characterized in thatthe substrate is a silica, silicon nitride, titanium, titanium nitride,tantalum or tantalum nitride surface.
 26. The process as claimed in oneor more of claims 21-25, characterized in that the substrate is part ofan electronic component.
 27. The use of a polybenzoxazole as claimed inclaim 14 as an insulating coat and/or protective coat for electroniccomponents.
 28. A composition comprising a polyhydroxyamide as claimedin one or more of claims 1-13 and an organic solvent, preferablyacetone, cyclohexanone, diethylene glycol monoethyl ether, diethyleneglycol diethyl ether, N-methylpyrrolidone, γ-butyrolactone, ethyllactate, tetrahydrofuran, methyl acetate or a mixture thereof.
 29. Thecomposition as claimed in claim 28, characterized in that it has apolyhydroxyamide content, based on the total composition, of 10-50% byweight, preferably 20-40% by weight, more preferably about 20% byweight.